CN106684367B - Low-temperature petroleum coke negative electrode material coated with nitrogen-containing polymer pyrolytic carbon and preparation method thereof - Google Patents
Low-temperature petroleum coke negative electrode material coated with nitrogen-containing polymer pyrolytic carbon and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a low-temperature petroleum coke negative electrode material with a surface coated with nitrogen-containing polymer pyrolytic carbon and a preparation method thereof, wherein the composite negative electrode material comprises low-temperature petroleum coke as an active substance and nitrogen-containing polymer pyrolytic carbon as a surface coating layer; the lithium ion battery using the composite petroleum coke negative electrode material prepared by the invention has the characteristics of high specific capacity, good cycle performance and the like, and the specific capacity of the composite material is higher than the theoretical specific capacity 372 mA.h.g of the graphite negative electrode material‑1The stable capacity can reach 400 mA.h.g‑1The above; the composite material has good cycle performance, and the capacity retention rate can be kept at about 60-90% after 300 cycles; the method provided by the invention has the advantages of simple operation, low cost, environmental friendliness, high capacity and the like.
Description
The invention relates to a low-temperature petroleum coke negative electrode material with a surface coated with nitrogen-containing polymer pyrolytic carbon and a preparation method thereof, belonging to the technical field of negative electrode materials of lithium ion batteries.
Background
Since the first commercialization by sony corporation in 1990, lithium ion batteries have been developed at a high speed for over 30 years, and have been widely used in place of nickel-hydrogen batteries and nickel-cadmium batteries in 3C digital fields represented by portable electric devices such as mobile phones and notebook computers. The large-scale application in the fields of electric vehicle power batteries and small-sized power station energy storage batteries is still in a starting or development stage, wherein the two most important reasons are the safety and the high-rate charge and discharge performance of the batteries. Here, the negative electrode material is an important factor affecting the safety and the high-rate charge and discharge performance of the lithium ion battery.
In view of the current situation, the lithium ion battery cathode materials in relatively mature markets at home and abroad mainly comprise artificial graphite represented by mesocarbon microbeads and graphite-like carbon cathode materials such as natural graphite coated by spheroidization and polymer pyrolytic carbon. The graphite carbon negative electrode material has the advantages of the potential of an embedded/separated lithium ion electrode close to 0V, stable charge-discharge potential platform, high specific capacity, low cost and other good comprehensive properties, and is still the most widely applied negative electrode material.
Graphite as a negative electrode material of a lithium ion battery has some defects, for example, lithium ions can only be deintercalated through the boundary of a flake graphite layer, the relative reaction area is small, the diffusion path in the deintercalation process of the lithium ions of the graphite flake layer is long, the large-current charging performance is not ideal, and in overcharge, the deposition of lithium metal on a graphite electrode is likely to occur due to the fact that the intercalation potential is close to 0V, so that the potential safety hazard exists. Therefore, a cathode material with excellent rate performance, high safety performance and low cost is found, and is very important for the large-scale application of the lithium ion battery as a power source of the electric vehicle.
The petroleum coke has a disordered layer structure and has an inclined voltage change curve in the charging and discharging process, so that the charging and discharging state of the battery can be judged; and because the diffusion path of lithium ions is short, the lithium ion battery is superior to the high-rate charge-discharge performance of graphite carbon negative electrode materials, and therefore, the lithium ion battery has important significance for the application of new energy power automobiles.
However, because the petroleum coke graphite structure treated at low and medium temperature (500 plus 2000 ℃) is deficient, the stable cyclic specific capacity is far lower than 372 mA.h.g-1The theoretical specific capacity of (a). Shuhua Ma et al (Solid State Ionics, 86-88 (1996); 911--1. Meanwhile, the petroleum coke treated by the low temperature and the medium temperature has wide treatment temperature range, and the crystallinity, the surface chemical state, the porosity and the aggregation of particles of the microcrystalThe state and distribution of the material are greatly different, and the industrial petroleum coke has complex element components and greatly different impurity contents or purities, so that the first coulombic efficiency of the material in a Solid Electrolyte Interface (SEI) stage, namely an electrode surface passivation film forming stage, is greatly different. These disadvantages severely restrict the industrial application of petroleum coke material as the negative electrode of lithium ion batteries, which is one of the important reasons why petroleum coke is not applied on a large scale in more than 30 years since the commercialization of lithium ion batteries.
Disclosure of Invention
The invention aims to provide a low-temperature petroleum coke negative electrode material with a surface coated with nitrogen-containing polymer pyrolytic carbon and a preparation method thereof, wherein low-temperature petroleum coke obtained by different methods is used as a raw material, and the surface coated with the nitrogen-containing polymer pyrolytic carbon is subjected to modification treatment, so that the reversible capacity and the cycle performance of the petroleum coke are improved to a certain extent; meanwhile, the first charge-discharge efficiency is correspondingly improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a low-temperature petroleum coke negative electrode material with a surface coated with nitrogen-containing polymer pyrolytic carbon is disclosed, wherein the low-temperature petroleum coke is used as an active substance, the nitrogen-containing polymer pyrolytic carbon is used as a surface coating material, and the surface of the composite material is of a porous structure.
The active substance is one or more than one of low-temperature petroleum cokes obtained by different methods;
the nitrogen-containing polymer is one or more of melamine, polyacrylonitrile, polyaniline, polyamide and polyimide;
the pyrolytic carbon is a product of the nitrogen-containing polymer after high-temperature carbonization;
the porous structure is a nitrogen-containing polymer pyrolytic carbon porous structure;
preferably, the size of the whole composite material is 0.5-20 μm, and the particle size of the active substance is 0.5-20 μm;
preferably, the nitrogen-containing polymeric pyrolytic carbon comprises 3-8wt.% of the entire composite.
A preparation method of a low-temperature petroleum coke negative electrode material with a surface coated with nitrogen-containing polymer pyrolytic carbon comprises the following steps:
(1) mixing low-temperature petroleum coke with a polymer and a solvent, and stirring to obtain a mixed solution;
(2) carrying out rotary evaporation separation on the solvent in the mixed solution obtained in the step (1) under a rotary evaporator;
(3) and (3) drying the mixture on the basis of the step (2), pre-oxidizing the dried mixture at a certain temperature, and sintering to obtain the petroleum coke negative electrode material with the surface coated with the nitrogen-containing polymer pyrolytic carbon.
Preferably, the temperature for processing the low-temperature petroleum coke is controlled below 1000 ℃;
as another preferred mode, the solvent is one or more of deionized water, ethanol, dimethylformamide, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, dichloromethane and the like;
as another preference, the pre-oxidation temperature is between 200 and 400 ℃, and the sintering temperature is between 500 and 900 ℃;
further preferably, the sintering step is followed by a grinding and sieving step.
The composite negative electrode material has certain porous structures, and the porous structures not only can reduce the deformation of the electrode, but also can provide a large contact area between an active substance and an electrolyte, and improve the diffusion rate of lithium ions, thereby further improving the electrochemical performance of the composite electrode.
The surface of the composite cathode material is coated with a layer of nitrogen-containing polymer pyrolytic carbon, the pyrolytic carbon film is of a porous carbon structure, and the structure can form a conductive network space, which is beneficial to conduction of electrons and mass transfer diffusion, so that the cycle performance of the composite cathode material is obviously improved.
Compared with the existing negative electrode material, the low-temperature petroleum coke negative electrode material with the surface coated with the nitrogenous polymer pyrolytic carbon shows a specific capacity 372 mA-h-g higher than that of the traditional graphite theory-1The stable capacity can reach 400 mA.h.g-1The above; the composite material shows good cycle performance, and the capacity retention rate is still kept after 300 cyclesCan be kept at about 60-90%; in addition, the method provided by the invention has the advantages of simple operation, low cost, environmental friendliness and the like.
Description of the drawings:
FIG. 1 is a scanning electron micrograph of a low-temperature petroleum coke negative electrode material (A1) coated with polyacrylonitrile pyrolytic carbon prepared in example 1;
fig. 2 is a scanning electron micrograph of the low-temperature petroleum coke negative electrode material (a 2) coated with polyaniline pyrolytic carbon prepared in example 2;
FIG. 3 is a specific capacity-cycle number curve of the low-temperature petroleum coke negative electrode material (A1) coated with polyacrylonitrile pyrolytic carbon in the surface prepared in example 1;
fig. 4 is a specific capacity-cycle number curve of the low-temperature petroleum coke negative electrode material (a 2) coated with polyaniline pyrolytic carbon in the surface prepared in example 2;
FIG. 5 is a voltage-specific capacity curve of the low-temperature petroleum coke negative electrode material (A1) coated with polyacrylonitrile pyrolytic carbon in the surface prepared in example 1;
fig. 6 is a voltage-specific capacity curve of the low-temperature petroleum coke negative electrode material (a 2) coated with polyaniline pyrolytic carbon in the surface prepared in example 2;
FIG. 7 is a SEM of the low temperature petroleum coke feedstock (Y1) of comparative example 1;
FIG. 8 is a scanning electron micrograph of a low temperature sintered petroleum coke negative electrode material (Y2) of comparative example 2;
fig. 9 is a specific capacity-cycle number curve for comparative example 1 low temperature petroleum coke feedstock (Y1);
fig. 10 is a specific capacity-cycle number curve of the low-temperature sintered petroleum coke negative electrode material (Y2) of comparative example 2.
The specific implementation mode is as follows:
embodiments of the present invention will be described in detail below with reference to specific examples. The following examples are merely preferred embodiments of the present invention to facilitate a better understanding of the invention and therefore should not be considered as limiting the scope of the invention. Various modifications and changes may be made by those skilled in the art, and any modification, equivalent replacement or improvement made without departing from the spirit and principle of the present invention should be covered within the protection scope of the present invention.
Example 1:
(1) crushing industrial petroleum coke to a particle size of 0.1-1 mm, further crushing the industrial petroleum coke in a high-speed crusher, sieving the industrial petroleum coke with a 600-mesh sieve, and taking the lower fine powder as a raw material for utilization, wherein the experimental low-temperature petroleum coke raw materials are the fine powder and are marked as Y1;
(2) weighing 0.5 g of polyacrylonitrile, dissolving in 50 mL of N, N-dimethylformamide solution, adding 10 g of low-temperature petroleum coke raw material (Y1) after complete dissolution, performing magnetic stirring for 2 h, then performing reduced pressure rotary evaporation, drying the obtained rotary evaporated solid in an oven at 60 ℃ for 2 h, then placing in a muffle furnace for pre-oxidation treatment at 240 ℃ for 2 h, and placing the pre-oxidized sample in a N-channel2And (3) sintering the tubular furnace for 2 hours at 300 ℃, raising the temperature to 700 ℃ for sintering for 9 hours, taking out a sintered sample, grinding the sintered sample, and sieving the ground sample by a 800-mesh sieve to obtain the low-temperature petroleum coke negative electrode material with the surface coated with the polyacrylonitrile pyrolytic carbon, wherein the low-temperature petroleum coke negative electrode material is marked as A1.
(3) The particle size of the obtained low-temperature petroleum coke negative electrode material with the surface coated with polyacrylonitrile pyrolytic carbon is within the range of 0.5-20 μm, and a scanning electron microscope photo of the low-temperature petroleum coke negative electrode material is shown in figure 1.
And (3) electrochemical performance testing:
(1) according to the active substance (low-temperature petroleum coke with polyacrylonitrile pyrolytic carbon coated on the surface): conductive agent (acetylene black): weighing a binder (PTFE) =7:2:1 in a mass ratio, mixing and stirring uniformly by taking isopropanol as a solvent, rolling the mixture into sheets by a roll pair machine, then punching the sheets into round sheets with the diameter of 12 mm by a sheet punching machine, drying and weighing the round sheets at 120 ℃ for 3 hours, finally pressing the round sheets onto a current collector (nickel screen) to obtain an electrode sheet, and continuously drying the electrode sheet at 120 ℃ for 5 hours for later use;
(2) and placing the electrode plate into a glove box filled with argon, assembling the button half-cell according to the sequence of the negative electrode shell, the electrode plate, the electrolyte, the diaphragm, the electrolyte, the lithium plate, the gasket, the spring piece and the positive electrode shell, and testing the charge and discharge performance of the button half-cell in a Xinwei cell testing system after sealing. Here, the electrolyte is 1 mol. L-1LiPF of6And the + EC + DMC, the diaphragm is a polyethylene/propylene composite microporous membrane, the charging and discharging voltage range is 0.01-2.5V, the test is carried out under the multiplying power of 0.1C, the specific capacity-cycle times of the test half-cell are shown in figure 3, and the voltage-specific capacity curve is shown in figure 5.
Example 2:
(1) firstly weighing 0.6 g of ammonium persulfate to be dissolved in 20 mL of deionized water, and placing the solution in a separating funnel for later use;
(2) 0.2 g of aniline liquid is added dropwise to 50 mL1.2 mol.L-1Stirring the HCl solution, adding 8 g of low-temperature petroleum coke raw material, uniformly mixing, stirring for 2 h, transferring the mixture into a 250 mL three-neck flask, carrying out oil bath reflux at 80 ℃ for 2 h, cooling to room temperature, transferring the mixture into an ice-water bath, dropwise adding an ammonium persulfate solution into the mixed solution at a speed of 1 drop/second, carrying out suction filtration on the mixed solution, washing the mixed solution with deionized water for multiple times until the pH value is 7, drying the obtained filter residue in an oven at 60 ℃ for 2 h, and putting the dried filter residue into an N-containing tank2And (3) sintering the tubular furnace for 2 hours at 300 ℃, raising the temperature to 700 ℃ for sintering for 9 hours, taking out a sintered sample, grinding the sintered sample, and sieving the ground sample by a 800-mesh sieve to obtain the low-temperature petroleum coke negative electrode material with the surface coated with polyaniline pyrolytic carbon, wherein the low-temperature petroleum coke negative electrode material is marked as A2.
(3) The particle size of the obtained low-temperature petroleum coke negative electrode material coated with polyaniline pyrolytic carbon on the surface is within the range of 0.5-20 μm, and a scanning electron micrograph thereof is shown in figure 2.
And (3) electrochemical performance testing:
(1) according to the active substance (low-temperature petroleum coke with polyaniline pyrolytic carbon coated on the surface): conductive agent (acetylene black): weighing a binder (PTFE) =7:2:1 in a mass ratio, mixing and stirring uniformly by taking isopropanol as a solvent, rolling the mixture into sheets by a roll pair machine, then punching the sheets into round sheets with the diameter of 12 mm by a sheet punching machine, drying and weighing the round sheets at 120 ℃ for 3 hours, finally pressing the round sheets onto a current collector (nickel screen) to obtain an electrode sheet, and continuously drying the electrode sheet at 120 ℃ for 5 hours for later use;
(2) placing the electrode plate into a glove box filled with argon, assembling the button half-cell according to the sequence of the negative electrode shell, the electrode plate, the electrolyte, the diaphragm, the electrolyte, the lithium sheet, the gasket, the spring sheet and the positive electrode shell, sealing, and then placing the button half-cell in the glove boxAnd the Xinwei battery testing system is used for testing the charge and discharge performance of the button half battery. Here, the electrolyte is 1 mol. L-1LiPF of6And the + EC + DMC, the diaphragm is a polyethylene/propylene composite microporous membrane, the charging and discharging voltage range is 0.01-2.5V, the test is carried out under the multiplying power of 0.1C, the specific capacity-cycle times of the test half-cell are shown in figure 4, and the voltage-specific capacity curve is shown in figure 6.
Comparative example 1:
(1) according to active substances (low-temperature petroleum coke raw materials): conductive agent (acetylene black): weighing a binder (PTFE) =7:2:1 in a mass ratio, mixing and stirring uniformly by taking isopropanol as a solvent, rolling the mixture into sheets by a roll pair machine, then punching the sheets into round sheets with the diameter of 12 mm by a sheet punching machine, drying and weighing the round sheets at 120 ℃ for 3 hours, finally pressing the round sheets onto a current collector (nickel screen) to obtain an electrode sheet, and continuously drying the electrode sheet at 120 ℃ for 5 hours for later use;
(2) and placing the electrode plate into a glove box filled with argon, assembling the button half-cell according to the sequence of the negative electrode shell, the electrode plate, the electrolyte, the diaphragm, the electrolyte, the lithium plate, the gasket, the spring piece and the positive electrode shell, and testing the charge and discharge performance of the button half-cell in a Xinwei cell testing system after sealing. Here, the electrolyte is 1 mol. L-1LiPF of6+ EC + DMC, the diaphragm is polyethylene/propene compound microporous membrane, the range of charging and discharging voltage is 0.01-2.5V, the test is carried out under 0.1C multiplying power, and the test half-cell specific capacity-cycle number is shown in figure 9.
Comparative example 2:
(1) putting the low-temperature petroleum coke raw material into a reactor with N2The tubular furnace is sintered for 2 hours at 300 ℃, then is heated to 700 ℃ for sintering for 9 hours, a sintered sample is taken out for grinding and is sieved by a 800-mesh sieve, and the low-temperature sintered petroleum coke negative electrode material is obtained and is marked as Y2, and an electron microscope photo thereof is shown in figure 8.
And (3) electrochemical performance testing:
(1) according to the active material (low-temperature sintered petroleum coke negative electrode): conductive agent (acetylene black): weighing a binder (PTFE) =7:2:1 in a mass ratio, mixing and stirring uniformly by taking isopropanol as a solvent, rolling the mixture into sheets by a roll pair machine, then punching the sheets into round sheets with the diameter of 12 mm by a sheet punching machine, drying and weighing the round sheets at 120 ℃ for 3 hours, finally pressing the round sheets onto a current collector (nickel screen) to obtain an electrode sheet, and continuously drying the electrode sheet at 120 ℃ for 5 hours for later use;
(2) and placing the electrode plate into a glove box filled with argon, assembling the button half-cell according to the sequence of the negative electrode shell, the electrode plate, the electrolyte, the diaphragm, the electrolyte, the lithium plate, the gasket, the spring piece and the positive electrode shell, and testing the charge and discharge performance of the button half-cell in a Xinwei cell testing system after sealing. Here, the electrolyte is 1 mol. L-1LiPF of6+ EC + DMC, the diaphragm is polyethylene/propene compound microporous membrane, the range of charging and discharging voltage is 0.01-2.5V, the test is carried out under 0.1C multiplying power, and the test half-cell specific capacity-cycle number is shown in figure 10.
The charge and discharge performance of the lithium ion battery negative electrode materials A1, A2, Y1 and Y2 is shown in Table 1;
in table 1, the first coulombic efficiency is the ratio of the first lithium removal specific capacity/the first lithium insertion specific capacity;
table 1:
| material | First lithium intercalation specific capacity/mA.h.g-1 | First lithium removal specific capacity/mA.h.g-1 | First coulomb efficiency% | Lithium removal specific capacity/mA.h.g after 100 cycles-1 |
| A1 | 960.5 | 536.5 | 55.8 | 428.3 |
| A2 | 912.6 | 585.5 | 64.2 | 412.3 |
| Y1 | 1241.4 | 380.8 | 30.6 | 228.1 |
| Y2 | 796.2 | 486.6 | 61.1 | 346.2 |
As can be seen from Table 1:
the first discharge specific capacity of the low-temperature petroleum coke negative electrode materials A1 and A2 coated with the nitrogen-containing polymer pyrolytic carbon provided by the invention is higher than that of petroleum coke materials Y1 and Y2 which are not coated, and after 100 cycles, the capacity can still be maintained at 400 mA.h.g-1The cycle performance is obviously superior to Y1 and Y2, which shows that the low-temperature petroleum coke negative electrode material coated with the nitrogen-containing polymer pyrolytic carbon on the surface has the advantages of high specific capacity and good cycle performance.
Claims (4)
1. The low-temperature petroleum coke negative electrode material coated with nitrogen-containing polymer pyrolytic carbon is characterized by taking the surface as an active material
The low-temperature petroleum coke of the active substance and the nitrogenous polymer pyrolytic carbon as a surface coating material, wherein the treatment temperature of the low-temperature petroleum coke of the active substance is controlled below 1000 ℃;
the nitrogen-containing polymer is one or more of melamine, polyacrylonitrile, polyaniline, polyamide and polyimide;
the preparation method of the low-temperature petroleum coke negative electrode material with the surface coated with the nitrogen-containing polymer pyrolytic carbon comprises the following synthetic steps:
(1) mixing and stirring low-temperature petroleum coke with a polymer and solvent mixed solution to obtain a mixed solution;
(2) carrying out rotary evaporation separation on the solvent in the mixed solution obtained in the step (1) under a rotary evaporator;
(3) on the basis of the step (2), drying the mixture, pre-oxidizing at the temperature of 200-400 ℃, and then pyrolyzing and sintering to obtain a petroleum coke negative electrode material with the surface coated with nitrogen-containing polymer pyrolytic carbon;
the pre-oxidation temperature is 200-400 ℃, and the sintering temperature is 450-950 ℃;
the size of the negative electrode material is 0.5-20 μm, and the particle size of the active material particles is 0.5-20 μm;
the nitrogen-containing polymer pyrolytic carbon accounts for 3-8 wt% of the negative electrode material.
2. The low-temperature petroleum coke negative electrode material with the surface coated with nitrogen-containing polymer pyrolytic carbon as claimed in claim 1, wherein the negative electrode material is prepared by coating the surface with nitrogen-containing polymer pyrolytic carbon
Wherein the pyrolytic carbon is the product of high-temperature carbonization of the nitrogen-containing polymer according to claim 1.
3. The low-temperature petroleum coke negative electrode material with the surface coated with nitrogen-containing polymer pyrolytic carbon as claimed in claim 1, which is characterized by comprising the following synthesis steps:
(1) mixing and stirring low-temperature petroleum coke with a polymer and solvent mixed solution to obtain a mixed solution;
(2) carrying out rotary evaporation separation on the solvent in the mixed solution obtained in the step (1) under a rotary evaporator;
(3) and (3) drying the mixture on the basis of the step (2), pre-oxidizing the dried mixture at the temperature of 200-400 ℃, and then pyrolyzing and sintering the dried mixture to obtain the petroleum coke negative electrode material of which the surface is coated with the nitrogen-containing polymer pyrolytic carbon.
4. The preparation method of the low-temperature petroleum coke negative electrode material with the surface coated with the nitrogen-containing polymer pyrolytic carbon according to claim 1
The method is characterized in that the solvent is one or more of deionized water, ethanol, dimethylformamide, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone and dichloromethane.
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